Tertiary phosphanes containing alkylene glycol groups

ABSTRACT

A compound is disclosed having the formula (I), in which m equals 1 to 1000; x equals 0 to 4; W is a group of formulas --CH 2  --CH 2  --, --CH(CH 3 )CH 2  -- or --CH 2  CH(CH 3 )--; R is hydrogen, a straight-chain or branched-chain C 1  -C 5  alkyl radical; or a group of formulas (a) or (b), in which a, b, c, d and e independently represent a number from 0 to 1000, at least one of the numbers represented by a, b, c, d and e being higher than 0; R 5 , R 6 , R 7 , R 8  and R 9  are the same or different and represent hydrogen, C 1  -C 5  alkyl or a group of formula (c); R 1  and R 2  are the same or different and represent a straight-chain, a branched-chain or a cyclic C 1  -C 30  alkyl radical or C 6  -C 10  aryl radical which is non-substituted or substituted by one to five C 1  -C 3  alkyl radicals, or R 1  and R 2  form together with the trivalent P atom form a dibenzophospholyl of formula (d) or a 3,4-dimethylphospholyl of formula (e); and L stands for C 1  -C 5  alkyl, C 1  -C 5  alkoxy, NO 2 , NR 3  R 4 , R 3  and R 4  independently representing hydrogen or C 1  -C 4  alkyl, or for Cl or OH. ##STR1##

This application is the national phase of PCT/EP97/03927, filed Jul. 21,1997, now WO98/04568.

The present invention is in the field of organic phosphorus chemistry.

The invention relates to novel tertiary phosphines carrying alkyleneglycol groups and to their preparation by nucleophilic substitution.

Complex compounds which contain, as central atom, a metal from subgroup8 of the Periodic Table of the Elements and, as ligands, P(III)compounds, e.g. phosphines or phosphites, and optionally further groupsable to form complexes, have been used increasingly in recent years ascatalysts for syntheses in organic chemistry. For example, the reactionof olefins with synthesis gas to give aldehydes (hydroformylation),which is carried out industrially on a large scale, is carried out inthe presence of catalyst systems consisting of cobalt and, inparticular, rhodium and triphenylphosphine. Also, for the reaction ofmethanol with synthesis gas to give higher alcohols (homologization),catalysts based on complex compounds containing phosphine have provensuccessful. In most of the above cases, the ligands are present inexcess, so that the catalyst system consists of complex compound andfree ligand. Depending on the solubility of the catalysts in organicmedia, the reactions take place in homogeneous phase.

Instead of in homogeneous phase, it is also possible to carry out thereaction in heterogeneous, multiphase reaction systems. An advantage ofthis process variant is the simple and gentle separation of the catalystdissolved in water from the water-insoluble reaction product. Thisprinciple is used, for example, in the process described in DE-C2-27 00904 for the preparation of nitriles by the addition reaction of hydrogencyanide to unsaturated organic compounds containing at least oneethylenic double bond. In the preparation of aldehydes by reaction ofolefins with carbon monoxide and hydrogen according to the processdescribed in DE-C2-26 27 354, rhodium in metallic form or in the form ofits compounds together with a water-soluble phosphine, e.g. the alkalimetal salt of tri(m-sulfonatophenyl)phosphine ("TPPTS") is used ascatalyst. Other examples of reactions with a heterogeneous catalystphase can be found in Agnew. Chem. 1993, 105, 1588 ff.

J. Chem. Soc., Perkin Trans. 1 1996, 1467, discloses chiral phosphineligands which are used for the asymmetric Grignard cross-coupling. Chem.Abstracts, Vol. 125, no. 33125x, describes phosphine compounds whichcontain three polyether radicals per phosphorus atom. J. Organ. Chem.1980, 1156 and Chem. Abstracts. Vol. 105, no. 60677x refer tobiphosphine compounds bridged via a polyether chain.

Two-phase processes have also proven highly successful on an industrialscale. Recent work has further improved the processes. For example,attempts are being made to increase the activity of the catalysts bymodifying the complex ligands and to extend their effectiveness in orderto further reduce the specific catalyst requirement, both metal andligand, and thus the product costs. Economic reasons are also a decisivefactor in working toward a significant reduction in the phosphine/metalratio. Finally, there are efforts to solve the product-specific problemsassociated with known processes. Moreover, the search is on for novelfields of application for these versatile catalyst systems.

The object of the present invention was to provide novel phosphineswhich are suitable, in particular, for use in catalyst systems fororganic syntheses.

The present invention provides tertiary phosphines of the formula (I)##STR2## in which m is a number from 2 to 300, preferably from 2 to 100;

y is a number from 0 to 4, preferably 0 or 1;

a, b, c, d and e independently of one another are numbers from 0 to1000, at least one of the numbers a, b, c, d and e being greater than 0;

R⁵, R⁶, R⁷, R⁸, and R⁹ are identical or different and are hydrogen, C₁-C₅ -alkyl or a group of the formula ##STR3## R¹ and R² are identical ordifferent and are a straight-chain, branched or cyclic C₁ -C₃₀ -alkylradical or C₆ -C₁₀ -aryl radical, which is unsubstituted or substitutedby from one to five C₁ -C₃ -alkyl radicals, or R¹ and R², together withthe trivalent P atom, form a dibenzophospholyl of the formula ##STR4##or a 3,4-dimethylphospholyl of the formula ##STR5## L is C₁ -C₅ -alkyl,C₁ -C₅ -alkoxy, NO₂, NR³ R⁴, where R³ and R⁴ independently of oneanother are hydrogen or C₁ -C₄ -alkyl, or L is Cl or OH and

x is a number from 0 to 4, preferably 0 or 1.

The alkylene glycol groups on the phenyl ring can be in the ortho, metaor para position relative to the phosphorus atom. The oxalkylene chainon which the group --(W--O--)_(m) is based can consist exclusively ofethylene oxide units or exclusively of propylene oxide units or of acombination of these units in any desired order.

Of particular interest are compounds of the formula (I) in which R¹ andR² are identical and are each a straight-chain or branched C₁ -C₆ -alkylradical, a cyclohexyl radical or a phenyl radical.

Also of particular interest are compounds of the formula (I) in which Ris hydrogen, methyl, ethyl, n-propyl, n-butyl or a group of the formula##STR6## in which c¹, d¹ and e¹ independently of one another are anumber from 1 to 500, in particular from 2 to 300, and

R⁷⁰, R⁸⁰ and R⁹⁰ are identical or different and are hydrogen, methyl,ethyl, n-propyl or n-butyl.

Also of particular interest are compounds of the formula (I) in which Lis methoxy, ethoxy, methyl, ethyl or OH, or in which x is 0.

Examples of compounds of the formula (I) are

methyl triphenylphosphin-4-yl triethylene glycol ether,

methyl triphenylphosphin-3-yl triethylene glycol ether,

methyl triphenylphosphin-2-yl triethylene glycol ether,

and compounds containing relatively long oxalkyl chains, the ethoxy andpropoxy units being in any desired order and usually forming a productmixture: ##STR7## in which m₁ and m₂ are each about the number 16 and Phis phenyl; ##STR8## in which m₃ is a number of about 22; ##STR9## inwhich m₄ is about 84 and m₅ is about 21, ##STR10## in which m₆ is about22 and m₇ is 5.5, ##STR11## in which m' is about 10, m" is from about 2to 3, m'" is from about 7 to 8 and m"" is about 30.

The distribution of the oxalkylene groups in the product, in particularthe ratio and the arrangement (order) of oxethylene to ox-2-propylenegroups is determined by the starting materials used. The latter areprepared by the addition reaction of ethylene oxide and propylene oxideto water or alcohols. The addition and arrangement takes place randomly.The starting materials used are commercial products from Hoechst AG.

The invention also provides a process for the preparation of a compoundof the formula (I) which comprises deprotonating ahydroxyphenylphosphine of the formula (II) ##STR12## using a base togive the corresponding phenoxide, and reacting it with a compound of theformula (III)

    X--(--W--O--).sub.m --R                                    (III)

in which W, R and m are as defined above and X is a nucleophilicallysubstitutable leaving group, to give the compound of the formula (I).

Examples of the nucleophilically substitutable leaving group X areortho-, meta- or para-toluenesulfonate, methanesulfonate,trifluoroacetate, trifluoromethanesulfonate, nonafluorobutylsulfonate,benzenesulfonate, p-nitrobenzenesulfonate, Cl, Br or I.

Suitable bases are, for example, NaOH, KOH, NaH, KH or trialkylamines.Preference is given to NaH, KH, triethylamine and KOH.

The reaction is expediently carried out at temperatures between 20 and100° C., preferably between 60 and 90° C. Since the deprotonation stepis usually exothermic, at this point in the synthesis, cooling may beexpedient, for example to from 0 to 20° C.

The process according to the invention can be carried out in thepresence or absence of organic solvents. Suitable organic solvents are,in particular, dimethylformamide, toluene or ethyl acetate. It isfurther advantageous to carry out the reaction according to theinvention under an inert-gas atmosphere.

The compounds of the formula (II) can be prepared by methods known fromthe literature, for example in accordance with O. Neunhoeffer et al.,Chem. Ber. 94 (1961), 2514.

The compounds of the formula (I) are suitable as ligands inmetal-complex-catalyzed organic reactions or as stabilizers forpolyalkylene glycols.

In the examples below, "TLC" means thin-layer chromatogram, "GC" meansgas chromatogram, "EE" means ethyl acetate and "DMF" meansdimethylformamide.

EXAMPLE 1 Triphenylphosphin-4-yl Triethylene Glycol Methyl Ether

    ______________________________________                                        Materials:                                                                    ______________________________________                                        200 g (0.7195 mol)                                                                        p-hydroxytriphenylphosphine                                                                     278 g/mol                                          18 g (0.75 mol) sodium hydride  24 g/mol                                     265 g (0.75 mol) p-tosyl triethylene glycol (90% strength)                     methyl ether                                                               ______________________________________                                         Procedure Protectivegas technique                                        

200 g of p-hydroxytriphenylphosphine are dissolved in 1 liter of DMF.Sodium hydride is added slowly in portions (exothermic), as a result ofwhich hydrogen begins to evolve. The mixture is stirred for 1 hour atroom temperature. 265 g of p-tosyl triethylene glycol methyl ether (90%strength) are added to the mixture, which is then stirred for 1 hour at80° C. The reaction is monitored from the TLC (eluent:EE/n-heptane=1/1).

Work-up

The solvent is removed under a high vacuum, and 1 liter of water and 2liters of tert-butyl methyl ether are added to the residue. The organicphase is separated off. The aqueous phase is extracted by shaking with2×500 ml of tert-butyl methyl ether. The combined organic phases aredried over Na₂ SO₄, filtered and reduced by evaporation.

TLC check: Eluent:

EE/n-heptane 1/1

Product: R_(f) =0.7

Tosyl ether: R_(f) =0.4

The crude product is applied to 1.2 times the amount by weight of silicagel and chromatographed over a column.

Column chromatography: 2 kg of silica gel, eluent EE/n-heptane 1/1

Yield: ˜70% of theory of colorless, very viscous oil

³¹ P-NMR (CD₂ Cl₂): -5.0 ppm ##STR13##

EXAMPLE 2 Triphenylphosphin-3-yl Triethylene Glycol Methyl Ether

    ______________________________________                                        Materials:                                                                    ______________________________________                                        200 g (0.7195 mol)                                                                        m-hydroxytriphenylphosphine                                                                     278 g/mol                                          18 g (0.75 mol) sodium hydride  24 g/mol                                     265 g (0.75 mol) p-tosyl triethylene glycol (90% strength)                     methyl ether                                                               ______________________________________                                         Procedure: Protectivegas technique                                       

200 g of m-hydroxytriphenylphosphine are dissolved in 1 liter of DMF.Sodium hydride is added slowly in portions (exothermic), as a result ofwhich hydrogen begins to evolve. The mixture is stirred for 1 hour atroom temperature. 265 g of p-tosyl triethylene glycol methyl ether (90%strength) are added to the mixture, which is then stirred for 1 hour at80° C. The reaction is monitored from the TLC (eluent:EE/n-heptane=1/1).

Work-up

The solvent is removed under a high vacuum, and 1 liter of water and 2liters of tert-butyl methyl ether are added to the residue. The organicphase is separated off. The aqueous phase is extracted by shaking with2×500 ml of tert-butyl methyl ether. The combined organic phases aredried over Na₂ SO₄, filtered and reduced by evaporation.

TLC check:

Eluent: EE/n-heptane 1/1

Product: R_(f) =0.7

Tosyl ether: R_(f) =0.4

The crude product is applied to 1.2 times the amount by weight of silicagel and chromatographed over a column.

Column chromatography: 2 kg of silica gel, eluent EE/n-heptane 1/1

Yield: ˜70% of theory of colorless, very viscous oil

³¹ P-NMR (CD₂ Cl₂): -5.1 ppm ##STR14##

EXAMPLE 3 (Triphenylphosphin-2-yl) Triethylene Glycol Methyl Ether

    ______________________________________                                        Materials:                                                                    ______________________________________                                        200 g (0.7195 mol)                                                                        o-hydroxytriphenylphosphine                                                                     278 g/mol                                          18 g (0.75 mol) sodium hydride  24 g/mol                                     265 g (0.75 mol) p-tosyl triethylene glycol (90% strength)                     methyl ether                                                               ______________________________________                                         Procedure: Protectivegas technique                                       

200 g of o-hydroxytriphenylphosphine are dissolved in 1 liter of DMF.Sodium hydride is added slowly in portions (exothermic), as a result ofwhich hydrogen begins to evolve. The mixture is stirred for 1 hour atroom temperature. 265 g of p-tosyl triethylene glycol methyl ether (90%strength) are added to the mixture, which is then stirred for 1 hour at80° C. The reaction is monitored from the TLC (eluent:EE/n-heptane=1/1).

Work-up

The solvent is removed under a high vacuum, and 1 liter of water and 2liters of tert-butyl methyl ether are added to the residue. The organicphase is separated off. The aqueous phase is extracted by shaking with2×500 ml of tert-butyl methyl ether. The combined organic phases aredried over Na₂ SO₄, filtered and reduced by evaporation.

TLC check:

Eluent: EE/n-heptane 1/1

Product: R_(f) =0.7

Tosyl ether: R_(f) =0.4

The crude product is applied to 1.2 times the amount by weight of silicagel and chromatographed over a column.

Column chromatography: 2 kg of silica gel, eluent EE/n-heptane 1/1

Yield: ˜70% of theory of colorless, very viscous oil

³¹ P-NMR (CD₂ Cl₂): -23 ppm ##STR15##

Preparation of p-toluenesulfonyl Triethylene Glycol Methyl Ether

200 g of p-toluenesulfonyl chloride and 172.4 g of triethylene glycolmonomethyl ether are dissolved in 1 liter of dichloromethane and cooledto 0° C. With vigorous stirring, 236.3 g of freshly powdered potassiumhydroxide are metered in at a rate such that the temperature does notexceed 5° C. The mixture is maintained at 0° C. for 3 hours. 1 liter ofdichloromethane and 1.2 liters of iced water are added. If more solidsform, a further 0.5 liter of iced water are added. The organic phase isseparated off and washed with 0.3 liter of saturated sodium chloridesolution. It is dried over Na₂ SO₄ and evaporated to dryness underreduced pressure.

Yield: 313.4 g; GC: 92.6% strength

EXAMPLE 4 Preparation of p-(P41/300)-triphenylphosphine

P41/300 is taken to mean a pentaerythritol etherified with ethyleneoxide and propylene oxide in a molar ratio of 4:1, the product having aviscosity of 300 mPa.s and about 84 ethoxy and about 21 propoxy groups.

28.33 g (101.8 mmol) of p-hydroxytriphenylphosphine are dissolved in 40ml of DMF. 101.8 mmol of potassium hydroxide are added, and the mixtureis heated at 80° C. for 1 hour. 509 g (102 mmol) of P41/300-tosylate arethen added, and the mixture is stirred for 2 hours at 80° C., the DMFthen being evaporated off under reduced pressure. The product iscompletely soluble in water at 50° C. It emulsifies in water attemperatures <20° C. and >80° C. The process is reversible.

³¹ P-NMR (CD₂ Cl₂): -5.2 ppm

EXAMPLE 5 Preparation of m-(P41/300)-triphenylphosphine

28.33 g of m-hydroxytriphenylphosphine are dissolved in 40 ml of DMF.101.8 mmol of potassium hydroxide are added, and the mixture is heatedat 80° C. for 1 hour. 509 g (102 mmol) of P41/300-TOS are then added,and the mixture is stirred for 2 hours at 80° C. The product iscompletely soluble in water at 50° C. It emulsifies in water attemperatures <20° C. and >80° C. The process is reversible.

³¹ P-NMR (CD₂ Cl₂): -5.1 ppm

EXAMPLE 6 Preparation of o-(P41/300)-triphenylphosphine

28.33 g of o-hydroxytriphenylphosphine are dissolved in 40 ml of DMF.101.8 mmol of potassium hydroxide are added, and the mixture is heatedat 80° C. for 1 hour. 509 g (102 mmol) of P41/300-TOS are then added,and the mixture is stirred for 2 hours at 80° C. The product iscompletely soluble in water at 50° C. It emulsifies in water attemperatures <20° C. and >80° C. The process is reversible.

³¹ P-NMR (CD₂ Cl₂): -23.5 ppm

Preparation of P41/300-tosylate

500 g of P41/300 and 19.07 g of p-toluenesulfonyl chloride are dissolvedin 1 liter of dichloromethane. 15.18 g of triethylamine are then added.The mixture is heated under reflux for 2 hours. 250 ml of water areadded to the reaction mixture, the aqueous phase is separated from theorganic phase, and the organic phase is dried with Na₂ SO₄.

Yield: 509.7 g

EXAMPLES 7 TO 16

General Preparation Procedure for the Feed Materials Used in Examples 7to 16

The polyalkylene glycols used in the general procedure are discussed inmore detail below.

PEG 200 is taken to mean a mixture of polyethylene glycols of theformula H(OCH₂ CH₂)_(m) OH in which m is an integer from 3 to 6, PEG 400is taken to mean a mixture of polyethylene glycols of the formula H(OCH₂CH₂)_(m) OH in which m is an integer from 7 to 10, PEG 600 is taken tomean a mixture of polyethylene glycols of the formula H(OCH₂ CH₂)_(m) OHin which m is an integer from 11 to 16, PEG 1000 is taken to mean amixture of polyethylene glycols of the formula H(OCH₂ CH₂)_(m) OH inwhich m is an integer from 15 to 30, and PEG 1500 is taken to mean amixture of polyethylene glycols of the formula H(OCH₂ CH₂)_(m) OH inwhich m is an integer from 25 to 35. Each of these mixtures is assigneda corresponding mean molecular weight of 200 (PEG 200), about 400 (PEG400), about CH₂ CH(CH₃) being 4:1. This mixture is assigned acorresponding mean molecular weight of 1000.

P41/300 is taken to mean a mixture of compounds of the formulaC{(OW)_(m) OH}₄, where m is an integer between 90 and 120 and W is agroup of the formulae --CH₂ CH₂ --, --CH(CH₃)CH₂ -- or --CH₂ CH(CH₃)--,the ratio of ethylene groups (--CH₂ CH₂ --) and methylethylene groups(CH₂ CH(CH₃) being 4:1. This mixture is assigned a corresponding meanmolecular weight of 5000.

B11/50 is taken to mean a mixture of compounds of the formula n-C₄ H₉--(OW)_(m) OH, where m is an integer between 11 and 21 and W is a groupof the formulae --CH₂ CH₂ --, --CH(CH₃)CH₂ -- or --CH₂ CH(CH₃)--, theratio of ethylene groups (--CH₂ CH₂ --) and methylethylene groups(--CH(CH₃)CH₂ -- or --CH₂ CH(CH₃)--) being 1:1. This mixture is assigneda corresponding mean molecular weight of 1700.

In the formulae, m is in each case an average value, meaning that theformula given has the mean molecular weight of the particular substanceclass.

1. O-Methyl-polyalkylene glycol ether ##STR16##

General procedure: 4.7 g (60 mmol) of methanesulfonyl chloride are addedto 50 mmol of polyalkylene glycol dissolved in 500 ml ofdichloromethane; 10.4 ml (75 mmol) of triethylamine are then addeddropwise at room temperature with stirring. Polyalkylene glycol may betaken to mean the compounds discussed above. The reaction solution isleft to stand for about 16 hours at room temperature [in the case of (e)for 8.5 hours under reflux].

(a) O-Mesyl-[M 350] ##STR17##

Feed: 0.2 mol of M 350, (molecular weight ˜350)

Yield: 83 g (97.5%), viscous oil

TLC, R_(f) =0.6 (CH₂ Cl₂ :C₂ H₅ OH=9:1)

¹ H-NMR: (CDCl₃) δ [ppm] 3.08 (OSO₂ CH₃, s 3H), 3.38 (OCH₃, s 3H),3.52-4.40 (OCH₂, m about 32)

Free OH function no longer present (acetic anhydride/pyridine method)

(b) O-Mesyl-[M 500] ##STR18##

Feed: 0.2 mol of M 500, (molecular weight ˜500)

Yield: 111.6 g (97%), viscous oil

TLC, R_(f) =0.5 (CH₂ Cl₂ :C₂ H₅ OH=9:1)

¹ H-NMR: (CDCl₃) δ [ppm] 3.08 (OSO₂ CH₃, s 3H), 3.38 (OCH₃, s 3H),3.52-4.40 (OCH₂, m about 45H)

Free OH function no longer present (acetic anhydride/pyridine method)

(c) O-Mesyl-[M 750] ##STR19##

Feed: 0.1 mol of M 750, (molecular weight ˜750)

Yield: 82.8 g (97.5%), viscous oil

TLC, R_(f) =0.59 (CH₂ Cl₂ :C₂ H₅ OH=9:2)

¹ H-NMR: (CDCl₃) δ [ppm] 3.08 (OSO₂ CH₃, s 3H), 3.38 (OCH₃, s 3H),3.52-4.40 (OCH₃, m about 68H)

Free OH function no longer present (acetic anhydride/pyridine method)

(d) O-Mesyl-[M 41/40] ##STR20##

Feed: 0.1 mol of M 41/40, (molecular weight ˜1000)

Yield: 99.6 g (92.6%), viscous oil

¹ H-NMR: (CDCl₃) δ [ppm] 3.08 (OSO₂ CH₃, s 3H), 3.38 (OCH₃, s 3H), 1.15and 1.38 (CCH₃, 2d 12H), 3.35-4.40 (OCH₂ and OCH, m about 80H)

Free OH function no longer present (acetic anhydride/pyridine method)

(e) O-Mesyl-[B 11/50] ##STR21##

Feed: 0.1 mol of B 11/50, (molecular weight ˜1700)

Yield: 173 g (97%), viscous oil

¹ H-NMR: (CDCl₃) δ [ppm] 0.92 (Bu CH₃, t 3H), 1.15 and 1.38 (CCH₃, CCH₂CH₂ C, m 55H), 3.08 (OSO₂ CH₃, "s" 3H), 3.35-4.40 (OCH₂ and OCH, m about121H)

Free OH function no longer present (acetic anhydride/pyridine method)

2. O-Mesyl-polyethylene glycols ##STR22## [(R=H and/or CH₃)]

General procedure: 11.46 g (100 mmol) of methanesulfonyl chloride areadded to 100 mmol of polyethylene glycol dissolved in 1000 ml ofdichloromethane; 12.2 g (120 mmol) of triethylamine are then addeddropwise at 0° C. with stirring. The reaction solution is then left tostand at room temperature for about 16 hours. For work-up, the reactionsolution is washed with 3×200 ml of 5% strength aqueous citric acid,with 2×200 ml of saturated sodium hydrogencarbonate solution and oncewith 200 ml of water. The dichloromethane phase is then dried withmagnesium sulfate, and the solvent is evaporated off. The reactionproduced consists of a mixture of starting polyalkylene glycol, mono-and dimesylated polyalkylene glycol; the desired monomesylated productcan be separated off by column chromatography (silica gel). (SeeExamples).

To ensure the structures of the target compounds and the purities, theproton ratios in the ¹ H NMR spectra and the quantitative determinationof the OH concentration by the acetic anhydride/pyridine method(titration of the amount of acetic acid liberated), thin-layerchromatographic and HPLC methods were used.

The abbreviation R_(f) is the retention quotient in thin-layerchromatography (TLC).

(a) O-Mesyl-[PEG 200] ##STR23##

Feed: 0.5 mol of PEG 200, (molecular weight ˜200)

Purification: column chromatography [silica gel (φ=10 cm, h=100 cm)]CH₂Cl₂ then CH₂ Cl₂ :C₂ H₅ OH=18:2

Yield: 24 g (17.3%), viscous oil

TLC, R_(F) =0.37 (CH₂ Cl₂ :C₂ H₅ OH=9:1)

¹ H-NMR: (CDCl₃) d [ppm] 2.70 (OH, s 1H), 3.08 (OSO₂ CH₃, "s" 3H),3.58-4.40 (OCH₂, m about 18H)

One OH function/molecule still present (acetic anhydride/pyridinemethod)

(b) O-Mesyl-[PEG 600] ##STR24##

Feed: 0.17 mol of PEG 600, (molecular weight ˜600)

Purification: column chromatography [silica gel (φ=10 cm, h=100 cm)]CH₂Cl₂ then CH₂ Cl₂ :C₂ H₅ OH=18:2

Yield: 29.5 g (26%), viscous oil

TLC, R_(F) =0.36 (CH₂ Cl₂ :C₂ H₅ OH=9:1)

¹ H-NMR: (CDCl₃) δ [ppm] 2.73 (OH, s 1H), 3.08 (OSO₂ CH₃ ; s 3H),3.59-4.40 (OCH₂, m about 55H)

One OH function/molecule still present (acetic anhydride/pyridinemethod)

(c) O-Mesyl-[PEG 1000] ##STR25##

Feed: 0.1 mol of PEG 1000, (molecular weight ˜1000)

Purification: column chromatography [silica gel (φ=10 cm, h=100cm)]acetone

Yield: 32.2 g (30%), waxy product

TLC, R_(F) =0.34 (CH₂ Cl₂ :C₂ H₅ OH=5:1)

¹ H-NMR: (CDCl₃) δ [ppm] 2.65 (OH, s 1H), 3.08 (OSO₂ CH₃ ; s 3H),3.57-4.40 (OCH₂, m about 92H)

One OH function/molecule still present (acetic anhydride/pyridinemethod)

(d) O-Mesyl-[PEG 1500] ##STR26##

Feed: 0.1 mol of PEG 1500, (molecular weight ˜1500)

Purification: column chromatography [silica gel (φ=10 cm, h=100 cm)]acetone

Yield: 20 g (19%)

TLC, R_(F) =0.45 (CH₂ Cl₂ :C₂ H₅ OH=4:1)

¹ H-NMR: (CDCl₃) δ [ppm] 2.65 (OH, s 1H), 3.08 (OSO₂ CH₃ ; s 3H),3.57-4.40 (OCH₂, m about 135H)

One OH function/molecule still present (acetic anhydride/pyridinemethod)

(e) O-Mesyl-[P 41/300] ##STR27##

Feed: 0.01 mol of P 41/300, (molecular weight ˜5000)

Purification: as in the general procedure for O-mesyl-polyalkyleneglycol (1.)

Yield: 49.8 g (98%), viscous oil

TLC (RP 18), R_(F) =about 0.9 (CH₃ OH:CH₃ CN=7:3)

¹ H-NMR: (CDCl₃) δ [ppm] 1.14 (CCH₃, m about 65H), 2.80 (OH, s 3H), 3.08(OSO₂ CH₃ ; s 3H), 3.20-4.40 (OCH₂, OCH, m about 420H)

The reaction product still contains 3 OH functions in randomdistribution (acetic anhydride/pyridine method)

General Procedure for the Synthesis of4-(diphenylphosphinyl)phenoxy-polyalkylene Glycols and Ethers (Examples7 to 16) ##STR28##

General procedure: The following reaction is carried out under nitrogen.1.73 g (60 mmol) of NaH (80% strength) are initially introduced into 150ml of DMF, and 16.7 g (60 mmol) of diphenyl-4-hydroxyphenylphosphinedissolved in 100 ml of DMF are carefully added dropwise at roomtemperature. When the evolution of gas has stopped, 50 mmol ofO-mesyl-polyalkylene glycol dissolved in 50 ml of DMF are added, and themixture is heated at 90-100° C. for from 8 to 10 hours.

For work-up, the DMF is evaporated off under reduced pressure, and theresidue is taken up in 1000 ml of dichloromethane and washed with 3×250ml of 0.2N sulfuric acid and with 2×250 ml of water. The organic phaseis then dried over magnesium sulfate, and the solvent is evaporated off.

Purification of the reaction products: see Examples.

EXAMPLE 7 Preparation of 4-(diphenylphosphinyl)phenoxy-[M 350],Abbreviated to M350-TPP ##STR29##

Feed: 0.05 mol of O-mesyl-[M 350], (molecular weight ˜425)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=15:1

Yield: 23.6 g (75%), viscous oil

TLC, R_(F) =0.3 (CH₂ Cl₂ :C₂ H₅ OH=15:1)

¹ H-NMR: (CDCl₃) δ [ppm] 3.38 (OCH₃, s 3H), 3.52-4.20 (OCH₂, m about32H), 6.80-7.80 (arom. H, m about 14H)

³¹ P-NMR: 97% as phosphine and 3% as phosphine oxide

S<0.01%

EXAMPLE 8 Preparation of 4-(diphenylphosphinyl)phenoxy-[M 500],Abbreviated to (M 500-TPP) ##STR30##

Feed: 0.05 mol of O-mesyl-[M 500], (molecular weight ˜575)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=15:1

Yield: 32.3 g (83%), viscous oil

TLC, R_(F) =0.2 (CH₂ Cl₂ :C₂ H₅ OH=15:1)

¹ H-NMR: (CDCl₃) δ [ppm] 3.38 (OCH₃, s 3H), 3.52-4.20 (OCH₂, m about45H), 6.80-7.80 (arom. H, m about 14H)

³¹ P-NMR: 97% as phosphine and 3% as phosphine oxide

S 0.02%

EXAMPLE 9 Preparation of 4-(diphenylphosphinyl)phenoxy-[M 750],Abbreviated to (M750-TPP) ##STR31##

Feed: 0.04 mol of O-mesyl-[M 750], (molecular weight ˜825)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=15:1

Yield: 33.1 g (80%), viscous oil

TLC, R_(F) =0.27 (CH₂ Cl₂ :C₂ H₅ OH=15:1)

¹ H-NMR: (CDCl₃) δ [ppm] 3.38 (OCH₃, s 3H), 3.52-4.20 (OCH₂, m about69H), 6.80-7.80 (arom. H, m about 14H)

³¹ P-NMR: 97% as phosphine and 3% as phosphine oxide

S<0.01%

EXAMPLE 10 Preparation of 4-(diphenylphosphinyl)phenoxy-[M 41/40],Abbreviated to (M41/40-TPP) ##STR32##

Feed: 0.0212 mol of O-mesyl-[M 41/40], (molecular weight ˜1075)

Purification: column chromatography [silica gel (φ 4.5 cm, h 30 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=9:1

Yield: 18.6 g (68.5%), viscous oil

TLC, R_(F) =0.21 (CH₂ Cl₂ :C₂ H₅ OH=9:1)

¹ H-NMR: (CDCl₃) δ [ppm] 1.15 and 1.30 (CCH₃, 2d 12H), 3.38 (OCH₃, s3H), 3.36-4.20 (OCH₂, m about 80H), 6.80-7.80 (arom. H, m about 14H)

³¹ P-NMR: 93% as phosphine and 7% as phosphine oxide

S 0.08%

EXAMPLE 11 Preparation of 4-(diphenylphosphinyl)phenoxy-[B 11/50],Abbreviated to (B 11/50-TPP) ##STR33##

Feed: 0.02 mol of O-mesyl-[B 11/50], (molecular weight ˜1775)

Purification: column chromatography [silica gel (φ 4.5 cm, h 30 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then ethyl acetate:C₂ H₅ OH=20:1

Yield: 13.8 g (35%), viscous oil

¹ H-NMR: (CDCl₃) δ [ppm] 0.92 (Bu CH₃, t 3H), 1.15 and 1.38 (CCH₃, CCH₂CH₂ C, m 55H), 3.35-4.40 (OCH₂ and OCH, m about 121H), 6.80-7.80 (arom.H, m about 14H)

³¹ P-NMR: 82% as phosphine and 18% as phosphine oxide

S<0.01%

EXAMPLE 12 Preparation of 4-(diphenylphosphinyl)phenoxy-[PEG 200],Abbreviated to (PEG 200-TPP) ##STR34##

Feed: 0.054 mol of O-mesyl-[PEG 200], (molecular weight ˜280)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then ethyl acetate:C₂ H₅ OH=9:1

Yield: 19.0 g (75%), viscous oil

TLC, R_(F) =0.45 (CH₂ Cl₂ :C₂ H₅ OH=9:1)

¹ H-NMR: (CDCl₃) δ [ppm] 2.80 (OH, br. s 1H), 3.52-4.20 (OCH₂, m about20H), 6.86-7.70 (arom. H, m about 14H)

³¹ P-NMR: 96% as phosphine and 4% as phosphine oxide

S<0.01%

EXAMPLE 13 Preparation of 4-(diphenylphosphinyl)phenoxy-[PEG 600],Abbreviated to (PEG 600-TPP) ##STR35##

Feed: 0.022 mol of O-mesyl-[PEG 600], (molecular weight ˜680)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=18:1

Yield: 12.0 g (63%), viscous oil

TLC, R_(F) =0.35 (CH₂ Cl₂ :C₂ H₅ OH=9:1)

¹ H-NMR: (CDCl₃) δ [ppm] 2.80 (OH, br. s 1H), 3.56-4.20 (OCH₂, m about55H), 6.86-7.70 (arom. H, m about 14H)

³¹ P-NMR: 97% as phosphine and 3% as phosphine oxide

S<0.01%

EXAMPLE 14 Preparation of 4-(diphenylphosphinyl)phenoxy-[PEG 1000],Abbreviated to (PEG 1000-TPP) ##STR36##

Feed: 0.015 mol of O-mesyl-[PEG 1000], (molecular weight ˜1080)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=10:2

Yield: 9.2 g (50%), viscous oil

TLC, R_(F) =0.32 (CH₂ Cl₂ :C₂ H₅ OH=6:1)

¹ H-NMR: (CDCl₃) δ [ppm] 2.80 (OH, br. s 1H), 3.56-4.20 (OCH₂, m about75H), 6.86-7.70 (arom. H, m about 14H) (number of protons for PEG 1000fraction too low since during chromatographic purification the lowmolecular weight fractions have been isolated in preference; using HPLCanalysis, it is ensured that no 2 phosphine radicals are present permolecule in the product)

³¹ P-NMR: 96% as phosphine and 4% as phosphine oxide

S<0.01%

EXAMPLE 15 Preparation of 4-(diphenylphosphinyl)phenoxy-[PEG 1500],Abbreviated to (PEG 1500-TPP) ##STR37##

Feed: 0.0126 mol of O-mesyl-[PEG 1500], (molecular weight ˜1580)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=9:1

Yield: 10.2 g (46%), waxy product

TLC, R_(F) =0.35 (CH₂ Cl₂ :C₂ H₅ OH=6:1)

¹ H-NMR: (CDCl₃) δ [ppm] 2.80 (OH, br. s 1H), 3.56-4.20 (OCH₂, m about136H), 6.86-7.70 (arom. H, m about 14H)

³¹ P-NMR: 93% as phosphine and 7% as phosphine oxide

S<0.01%

EXAMPLE 16 Preparation of 4-(diphenylphosphinyl)phenoxy-[P 41/300],Abbreviated to (P 41/300-TPP) ##STR38##

Feed: 0.01 mol of O-mesyl-[P 41/300], (molecular weight ˜5080)

Purification: column chromatography [silica gel (φ 4.5 cm, h 50 cm)]first the ethyl acetate to remove diphenyl-4-hydroxyphenylphosphine andits phosphine oxide, then CH₂ Cl₂ to remove ethyl acetate, then CH₂ Cl₂:C₂ H₅ OH=10:1

Yield: 10.2 g (46%), viscous oil

TLC, R_(F) =0.56 (CH₂ Cl₂ :C₂ H₅ OH=3:1)

¹ H-NMR: (CDCl₃) δ [ppm] 1.14 (CCH₃, m about 65H), 3.56-4.20 (OCH₂, mabout 420H), 6.86-7.70 (arom. H, m about 14H)

³¹ P-NMR: 82% as phosphine and 18% as phosphine oxide

S<0.01%, P 0.52%

What is claimed is:
 1. A compound of the formula (I) ##STR39## in whichm is a number from 2 to 300;y is a number from 0 to 4; W is a group ofthe formulae --CH₂ --CH₂ --, --CH(CH₃)CH₂ -- or --CH₂ CH(CH₃)--; R ishydrogen, a straight-chain or branched C₁ -C₅ -alkyl radical; or a groupof the formulae ##STR40## where a, b, c, d and e independently of oneanother are numbered for 0 to 1000, at least one of the numbers a, b, c,d and e being greater than 0; R⁵, R⁶, R⁷, R⁸ and R⁹ are identical ordifferent and are hydrogen C_(1-C) ₅ -alkyl or a group of the formula##STR41## R¹ and R² are identical or different and are a straight-chain,branched or cyclic C₁ -C₃₀ -alkyl radical or C₆ -C₁₀ -aryl radical,which is unsubstituted or substituted by from one to five C₁ -C₃ -alkylradicals, or R¹ and R², together with the trivalent P atom, form adibenzophospholyl of the formula ##STR42## or a 3,4,-dimethylphospholylof the formula ##STR43## and L is C₁ -C₅ -alkyl, C₁ -C₅ -alkoxy, NO₂,NR³ R⁴, where R³ and and R⁴ independently of one another are hydrogen orC₁ -C₄ -alkyl, or L is Cl or OH, x is a number from 1 to 4, with provisothat when:R¹ and R² are both phenyl; Y is 0; W is --CH₂ --CH₂ --; R ishydrogen; and the group --O--(W--O)_(m) --R is in the para-positionrelative to phosphorus m is a number from 2 to 35; and the proviso thatwhen:R¹ and R² are both phenyl; Y is 0; W is --CH₂ --CH₂ --; R ismethyl; and the group --O--(W--O)_(m) --R is in the para-positionrelative to phosphorus m is a number from 2 to
 20. 2. A compound asclaimed in claim 1, wherein R is hydrogen, methyl, ethyl, n-propyl,n-butyl or a group of the formula ##STR44## in which c¹, d¹ and e¹independently of one another are a number from 1 to 500; and R⁷⁰, R⁸⁰and R⁹⁰ are identical or different and are hydrogen, methyl, ethyl,n-propyl or n-butyl.
 3. A compound as claimed in claim 1, wherein R¹ andR² are identical and are each a straight-chain or branched C₁ -C₆ -alkylradical, a cyclohexyl radical or a phenyl radical.
 4. A compound asclaimed in claim 1, wherein L is methoxy, ethoxy, methyl, ethyl or OH.5. A compound as claimed in claim 1, wherein y is
 0. 6. A compound asclaimed in claim 1, wherein m is a number from 2 to
 100. 7. A compoundas claimed in claim 2, in which c¹, d¹ and e¹ independently of oneanother are a number from 2 to
 300. 8. A process for the preparation ofa compound of the formula ##STR45## in which m is a number from 2 to300;y is a number from 0 to 4; W is a group of the formulae --CH₂ --CH₂--, --CH(CH₃)CH₂ -- or --CH₂ CH(CH₃)--; R is hydrogen, a straight-chainor branched C₁ -C₅ -alkyl radical; or a group of the formulae ##STR46##where a, b, c, d and e independently of one another are numbered for 0to 1000, at least one of the numbers a, b, c, d and e being greater than0;R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are hydrogen, C₁-C₅ -alkyl or a group of the formula ##STR47## R¹ and R² are identicalor different and are a straight-chain, branched or cyclic C₁ -C₃₀ -alkylradical or C₆ -C₁₀ -aryl radical, which is unsubstituted or substitutedby from one to five C₁ -C₃ -alkyl radicals, or R¹ and R², together withthe trivalent P atom, form a dibenzophospholyl of the formula ##STR48##or a 3,4,-dimethylphospholyl of the formula ##STR49## and L is C₁ -C₅-alkyl, C₁ -C₅ -alkoxy, NO₂, NR³ R⁴, where R³ and R⁴ independently ofone another are hydrogen or C₁ -C₄ -alkyl, or L is Cl or OH, x is anumber from 0 to 4, with proviso that when:R¹ and R² are both phenyl; Yis 0; W is --CH₂ --CH₂ --; R is hydrogen; and the group --O--(W--O)_(m)--R is in the para-position relative to phosphorus m is a number from 2to 35; and the proviso that when:R¹ and R² are both phenyl; Y is 0; W is--CH₂ --CH₂ --; R is methyl; and the group --O--(W--O)_(m) --R is in thepara-position relative to phosphorus m is a number from 2 to 20,whichcomprises deprotonating a hydroxyphenylphosphine of the formula (II)##STR50## wherein R¹, R², L and y are defined above, with a base to givethe corresponding phenoxide, and reacting it with a compound of theformula (III)

    X--(--W--O--).sub.m --R                                    (III),

in which W, R and m are defined above and X is a nucleophilic leavinggroup, to give a compound of the formula (I).
 9. The process as claimedin claim 8, wherein X is an ortho-, meta- or para-toluenesulfonate,methanesulfonate, trifluoroacetate, trifluoromethanesulfonate,nonafluorobutylsulfonate, benzenesulfonate, p-nitrobenzenesulfonate, Cl,Br or I.
 10. The process as claimed in claim 8, wherein the reaction iscarried out in the presence or in the absence of an organic solvent. 11.A process as claimed in claim 8, wherein m is a number from 2 to 100.